DE10392987T5 - Galvanic cell type chemical reaction system, method of activating this and method of reaction - Google Patents

Abstract

chemical Reaction system for performing chemical reactions of a target substance, which is a chemical reaction part comprising an oxygen ion conductor (ion conduction phase) and two electrodes, a cathode (reduction phase) and an associated anode (Oxidation phase), with the ionic conduction phase between them is composed of basic units, with microreaction areas, where oxidoreductions of a target substance take place, into one Part of the chemical reaction part are introduced by in one reducing atmosphere or under reduced pressure on the points of contact between the Ion conduction phase and an electron conduction phase resulting from a combination of any of an ionic conductor, an electron conductor or a mixed electric conductor, in chemical Reaction part applied current or voltage or a heat treatment is applied.

Description

The The present invention relates to a chemical reaction system of galvanic cell type and, more specifically, a chemical reaction system that efficiently removes nitrogen oxides from exhaust gas, containing oxygen, excludes. The present invention is useful in that it has a novel chemical reactor having microreaction regions, to perform of oxidation and reduction reactions on a target substance, in a part of the chemical reaction part of the above-mentioned chemical Reaction system introduced was so that oxygen and nitrogen oxides separated and from certain Structures in the above mentioned Microreaction regions are adsorbed from exhaust gas provides whereby the efficient processing of a target substance with low intake electrical energy allows becomes.

Furthermore The present invention relates to an energy-saving electrochemical reaction system and an activation procedure for this and more particularly relates to a chemical reaction system containing nitrogen oxides efficiently excludes exhaust gas containing, for example, oxygen, and a method of use and an activation method for this. The present invention is useful in that it is a new chemical reaction system together with a method of use and an activation method for this, wherein when the reactivity is through Adsorption of oxygen atoms at the surface during the exclusion of Nitrogen oxides from exhaust gas in the electrochemical reaction system has been reduced, the above-mentioned chemical reaction system can be reactivated at low energy consumption, creating a efficient chemical reaction of the target substance is made possible.

Furthermore The present invention relates to a reaction process in which an oxidoreduction reactor is used, and in particular a chemical reaction method for oxidizing, for example organic matter, organic chlorine compounds, hydrogen, Carbon monoxide, nitrogen oxides, ammonia and the like or chemical reaction process for reducing organic matter, Oxygen, water, nitrogen oxides and the like, in which an oxidoreduction reactor is used, which consists of a solid electrolyte in which it is is an oxygen ion conductor, and at least one electrode, which consists of an electron conductor composed. The present This invention is useful in that it provides a method for removing Nitrogen oxides from the exhaust gas of, for example, burners and the like, in which the above mentioned Oxidoreduct reactor is used.

Currently works the main method for eliminating nitrogen oxides, the produced by gasoline engines, with ternary catalysts. Because the exhaust from low-emission combustion engines and diesel engines, the one improved fuel consumption, but a surplus contains oxygen, is the reduction of catalytic activity due to the adsorption of oxygen through the surface of the ternary Catalyst a problem that prevents the exclusion of nitrogen oxides.

on the other hand is by applying a current flow to a solid electrolyte film with oxygen ion conductivity also achieved a distance without any adsorption of Oxygen from the exhaust gas is caused by a catalyst surface. In a proposal for a catalytic reactor is a system that simultaneously contains surface oxygen removed and decomposed nitrogen oxides into oxygen and nitrogen, by attaching to a solid electrolyte, between electrodes on both sides is inserted, voltage is applied.

It However, there is a problem that the adsorption probability the nitrogen oxides in the above-mentioned process, when in the exhaust gas, an excess oxygen, since the adsorption and decomposition reaction sites of oxygen and nitrogen oxides coexisting (coexist), consist of the same oxygen vacancies, due of both molecular selectivity and ratios of coexisting molecules much lower than that of the oxygen molecules, allowing a large current flow is necessary to split the nitrogen oxides, causing the uptake significantly increased electrical energy.

Under these circumstances, the inventors of the present invention had already discovered that it is possible in a chemical reactor to efficiently process a target substance with low electrical energy consumption by fabricating the internal structure of the cathode as a structure in which nanometer sized through-holes Top of one and the same layer are drawn and an electron conductor and an ionic conductor in the scale of nanometers to less than one micron are distributed together in a dense network, whereby the excess oxygen, which is a disturbing in the chemical reaction of the target substance gas is reduced (Japanese Patent Application 2001-225034). However, in this method, since oxygen molecules remaining in the treated gas that have passed through the upper portion of one and the same layer are still selectively adsorbed and split at the reaction sites, the amount of nitrogen oxides is still more strongly adsorbed the reduction of energy intake insufficient.

Furthermore Another problem with this method is that the Reduction in energy intake is inadequate as continuous Supplied with electricity must be to remove the coexisting oxygen molecules.

on the other hand is used in chemical reactions and in particular in oxidoreductions often a variety of catalysts, including catalysts of the homogeneous Catalysis and catalysts of heterogeneous catalysis, used. Compared with catalysts of homogeneous catalysis offer catalysts heterogeneous catalysis, solid catalysts such as Precious metals and zeolites, used, the advantage of the simple Separation of the reactant from the catalyst. Although catalysts the heterogeneous catalysis a simple separation of the catalyst enable, will still be needed Product, because the raw material and the reactive substance one and the same Room, of unreacted raw materials and by-products separated and cleaned. In a procedure that has been investigated is and does not require such separation and purification is it is a process that employs a reaction separation membrane (Kagaku Sosetsu No. 41, "Design of high function catalysts ", Japan Chemical Society (1999), p. 131).

For example, in a method employing a reaction separation membrane, when ethane is synthesized by an oxygen linkage reaction of methane using an oxygen-permeable membrane (3CH ₄ + 1 / 2O ₂ → C ₂ H ₄ + H ₂ O), CH ₄ and O _{2 is} separated by the oxygen permeable membrane and on the wall of the permeable membrane a suitable catalyst is placed on the CH ₄ side to form a system with CH ₄ , catalyst, oxygen permeable membrane and O ₂ , and O ₂ is passed through the catalyst the oxygen permeable membrane is activated to selectively synthesize ethane. When the same reaction is carried out using a hydrogen-permeable membrane, of course, the hydrogen-permeable membrane is disposed between the CH ₄ and the O ₂ in a system with CH ₄ , catalyst, hydrogen-permeable membrane and O ₂ ; however, a catalyst with methane dehydrogenation activity must be placed on the wall of the permeable membrane. Membranes used as reaction separation membranes are generally subdivided into porous membranes, metal membranes, ionic conductor membranes, mixed conductor membranes, and the like, according to the permeation mechanism of the permeated substance. Porous membranes that allow for selective permeation of molecules include zeolites and other membranes with nanopores; However, the synthesis of dense zeolite membranes without pinholes has not been proven.

From The metal membranes are made of Pd membranes and membranes from a Pd-Au alloy used as reaction separation membranes. Both will as hydrogen reaction separation membranes (hydrogen permeable membranes) used. The concentration difference (hydrogen partial pressure difference) between the two sides of the membrane is used as a driving force hydrogen permeable Membrane used. Ion conductor membranes (electrolyte membranes) are especially hydrogen ion conductors and oxygen ion conductors. If an ion conductor membrane is used as a reaction separation membrane As a result, electrodes are installed on both sides of the membrane and the electrodes become electrically connected to each other with electric wires because it is the driving force conducted by the ions is a gradient of the electric field. It comes to a movement of electrons through the guide wire (external circuit), because the ions pass through the membrane, while at the same time neutralize electrical charge. Exists in a mixed conductor membrane no requirement of electrodes and guidewires to send the electrons, since both ions and electrons (or holes) through the membrane can be passed. The concentration difference between the two sides of the membrane becomes meanwhile used as ion drive force.

In particular, in a reaction separation membrane using an ion conductor membrane, a reaction may proceed regardless of the concentration difference, since the gradient of the electric field is the driving force. However, electrodes are required and the electrodes use a stable substance with electron conductivity which is inactive in oxidation and reduction reactions. For example, noble metals such as Pt, Pd and the like, carbon and in oxidizing atmospheres LaCoO ₃ , LaFeO ₃ , LaMnO ₃ , LaCrO ₃ and other electron-conductive oxides and the like are used. In an example of a reaction separation membrane employing a hydrogen ion conductor membrane, trace amount of acetylene is removed by hydrogenation from ethylene. A reactor such as a C ₂ H ₄ , C ₂ H ₂ , Cu electrode, hydrogen ion conducting membrane, platinum black electrode and H ₂ reactor is constructed and electricity is applied between the two electrodes to selectively hydrogenate (reduce) acetylene, such that acetylene present as an impurity in the ethylene is converted to ethylene and removed. Such a reaction is due to the strong affinity between acetylene and the Cu electrode and the presence of atomic hydrogen, which is due to the Hydrogen ion conductor membrane was sent.

at an example of a reaction separation membrane in which a solid electrolyte membrane with oxygen ion conductivity is used, nitrogen oxides by reduction from exhaust gas away. In a reactor that has been proposed acts It is a system designed to simultaneously remove surface oxygen and decomposing nitrogen oxides into oxygen and nitrogen Applying voltage to a solid electrolyte between electrodes inserted on both sides has been developed. To the representation of the related art: In the literature of the state of Technique has been suggested on both sides with scandium oxide stabilized zirconium oxide to form platinum electrodes and strain to disassemble into nitrogen and oxygen (J. Electrochemical Soc. 122, 869 (1975)). In the literature of the prior art is also proposed on both sides of stabilized with yttria Zirconium oxide to form palladium electrodes and apply voltage in a mixed gas of nitrogen oxides, hydrocarbons and To split oxygen into nitrogen and oxygen (J. Chem. Soc. Faraday Trans. 91, 1995 (1995)). This way can at a Reaction separation membrane, in which an ion conductor membrane with electrodes provided and voltage is applied between the electrodes, wherein the gradient of the electric field is the driving force, not only the reaction independent from the concentration difference of the reacting substance or product expire; it will be as well the types of ions that pass through the ion conductor membrane at the Electrode activates and the molecules are easily attached to the interface split between the ion conductor and the electrode, so that the oxidation and the reduction can be easily carried out.

at a reaction method using a reaction separation membrane in which an ion conductor membrane is provided with electrodes and Voltage is applied between the electrodes, the gradient the electric field is the driving force, however, is the ability for oxidation and reduction high, but the selectivity low. When removing of nitrogen oxides in a reactor in which the above-mentioned ionic conductor is provided with electrodes, for example by reduction, if oxygen molecules These are also decomposed into oxygen ions, resulting in efficiency the removal of nitrogen oxides by reduction, which is the target the emission control is reduced. In addition, though one must simple oxidoreduction using a reducing agent or an oxidizing agent of suitable selectivity as well possible is, in this case, the reducing agent or the oxidizing agent Supplied funds or exchanged because the reaction can not progress, when this is used up.

Consequently In the light of the above-mentioned prior art, the inventors were able to do so of the present invention as a result of in-depth research on solution of these diverse problems when they discovered that one Reaction can be made more efficient if pairs of reaction sites to Carry out simultaneously occurring reduction reactions in a chemical Reaction part (for example, a arranged at the upper part of a cathode Working electrode layer) and the selective adsorbability in terms of oxygen molecules and nitrogen oxides is exploited.

The is called, that is an object of the present invention Invention is to overcome the above-mentioned problems of the state of Technology to solve and to provide a chemical reactor containing nitrogen oxides with low energy intake can efficiently exclude, with the decomposition Nitrogen oxide required amount of electricity by using Pairs of adsorptive Substances for oxygen molecules and nitric oxide molecules to facilitate the adsorption of nitrogen oxides, when in the exhaust excess oxygen is present, is reduced.

Furthermore In the light of the above-mentioned prior art, the inventors were able to do so of the present invention as a result of in-depth research, to the solution of these diverse problems when they discovered that it is possible was, oxygen molecules to ionize and remove and reactivate the system by in one in the upper part of a cathode in the chemical reaction part arranged working electrode layer local reaction sites, the greater efficiency of chemical reaction by simultaneously performing oxygen adsorption and allow adsorption-reduction reactions of nitrogen oxides, be formed and continue to adsorb a specified Amount of oxygen molecules Power is applied to the chemical reaction system.

That is, an object of the second embodiment of the present invention is to solve the above-mentioned problems and to provide a chemical reaction system in which the amount of electricity required for decomposing nitrogen oxides by simplifying the adsorption of nitrogen oxides by pairing substances having selective adsorptivity Oxygen molecules and nitrogen oxide molecules when excess oxygen is present in the exhaust gas is reduced, and in which the chemical reaction system is reactivated at the same time by applying current after adsorption of a fixed amount of oxygen and can exclude nitrogen oxides efficiently at low energy consumption.

Furthermore it is an object of the third embodiment of the present invention Invention, with the aim of introducing a new reaction process in an oxidoreduction reactor, which addresses the problems mentioned above solve the prior art may have been developed to provide a novel reaction process, wherein an oxidation or a reduction with high selectivity under Use of an oxidoreduction reactor without need of feeding or Replacing a reducing agent or oxidizing agent can be achieved.

When next the first embodiment of the present invention in more detail explained.

The The present invention relates to a chemical reaction system for Carry out chemical reactions of a target substance and this chemical reaction system consists of a chemical reaction part in which the above-mentioned chemical Reactions of the above mentioned Target substance performed and, preferably, a barrier layer for inhibiting ionization of oxygen.

Of the chemical reaction part for performing chemical reactions a target substance is preferably with a reduction phase, by feeding of electrons to elements contained in the target substance ions produces, an ionic conduction phase, the ions from the reduction phase conducts, and an oxidation phase, the electrons of ions, the were conducted by the ionic conduction phase, gives off, provided.

In The present invention is the target substance preferably nitrogen oxides in exhaust gas, and the nitrogen oxides are reduced in the reduction phase to produce oxygen ions, which are conducted in the ionic conduction phase. The target substance however, in the present invention is not to nitrogen oxides limited. In the chemical reactor of the present invention, carbon dioxide can be reduced to produce carbon monoxide from methane a mixed gas of hydrogen and carbon monoxide are produced or hydrogen can be produced from water.

The chemical reaction system may be in the form of, for example, a Pipe, a plate, a honeycomb or the like; preferably has However, it in particular one or more through holes with a pair of openings (like in a pipe or a honeycomb), wherein in each through hole chemical reaction sites are located.

at the above mentioned chemical reaction, the reduction phase is porous and should be the substance which is the target of the reaction, selectively adsorb. As elements contained in the reduction in the target substance electrons supplied be used to generate ions that transmit to the ion conduction phase are, the reduction phase is preferably made of an electrically conductive substance. For the purpose of promoting the transmission Of electrons and ions, it is desirable that they come from one conductive Mixed substance, which has the characteristics of both electron conduction as well as ionic conduction, or that they are made of a mixture made of an electron-conducting substance and an ion-conducting Substance exists. The reduction phase can be a layered structure have at least two or more phases of these substances.

The electrically conductive Substance and the ion-conducting substance serving as a reduction layer are not subject to any special restrictions. It can For example, platinum, palladium and other precious metals as well Nickel oxide, cobalt oxide, copper (I) oxide, lanthanum manganate, lanthanum cobaltite, Lanthanum chromite and other metal oxides as electrically conductive substance be used. Barium-containing oxides, zeolites and the like, which selectively adsorb the target substance can also serve as a reduction layer be used. Preferably, at least one or more of mentioned above Substances as a mixture with at least one or more used ion-conducting substances. Ion-conducting substances that can be used include, for example, stabilized with yttria or scandia Zirconium oxide and cerium (IV) oxide, lanthanum gallate or the like, stabilized with gadolinium oxide or samarium (III) oxide. It is also desirable that the reduction layer consists of a layer structure of at least two or more phases of the above-mentioned substances exist. Especially preferred the reduction layer consists of a layer structure of two Phases, an electrically conductive Phase, which consists of a precious metal like platinum or the like, and a mixed phase of nickel oxide or with yttria or scandium oxide stabilized zirconium oxide.

The ion conducting phase consists of a solid electrolyte with ion conductivity, and preferably a solid electrolyte with oxygen ion conductivity. Examples of solid electrolytes having oxygen ion conductivity include yttria or scandia stabilized zirconia and cerium (IV) oxide or gadolinia or Sa. marium (III) oxide stabilized lanthanum gallate; however, these are not limitations. It is preferred to use yttria or scandia stabilized zirconia which has excellent long term stability, high conductivity and strength.

The contains oxidizing phase a conductive substance, to cause ions from the ion conducting phase to be electrons be released. For the purpose of promoting the transmission of electrons and ions it is desirable the oxidizing phase consists of a mixed conductive substance containing the Features of both electron conductivity and ionic conductivity or from a mixture of an electron-conducting Substance and an ion-conducting substance. The electric conductive Substance and the ion-conducting substance acting as the oxidizing phase are not subject to any special restrictions. It can For example, platinum, palladium and other precious metals as well Nickel oxide, cobalt oxide, copper (I) oxide, lanthanum manganate, lanthanum cobaltite, Lanthanum chromite and other metal oxides as electrically conductive substance be used. As ion-conducting substance, for example, with yttrium oxide or scandium oxide stabilized zirconia or cerium (IV) oxide or gadolinia or samarium (III) oxide stabilized lanthanum gallate be used.

Around a supply of oxygen ions necessary to produce Electrons, if oxygen molecules oberflächenadsorbiert have been avoided, the barrier layer comprises such a material and such a structure, which prevent electrons from fed chemical reaction part and in particular that the reduction phase reaches the surface. This barrier layer is preferably an ionic conductor, electric mixed conductor or insulator, and if it is a is electric mixed conductor, is the proportion of electron conductivity preferably extremely low, because the preventing effect on the electron conduction when the electron conductivity is high, is diminished.

One A feature of the present invention is that microreaction regions, where oxidoreductions of a target substance take place, into one Part of the chemical reaction part are introduced by in one reducing atmosphere or under reduced pressure to the points of contact between the ion conduction phase and the electron conduction phase, which is from a combination of any of an ionic conductor, an electron conductor, and composed of an electric mixed conductor, electricity or an electric Field created or a heat treatment is applied. In the present invention, the features include forming the above-mentioned Microreaction areas of interfaces made of metal phases the electron conduction phase, oxygen-poor parts of the ion conduction phase and micro rooms (Intervals), the the contacts of this surrounded, in places of contact between the electron conduction phase and the ion conduction phase, the introduction of the mentioned above Microreaction areas where the above-mentioned oxidoreductions take place into the cathode, forming a working electrode layer for Rules for Oxidoreduction in the Upper Part of the Cathode and Introduction of Microreaction areas ranging in size from nanometers to a micrometer, where the above mentioned Oxidoreductions take place in this layer.

The working electrode disposed in the upper part of the cathode within the chemical reaction part has a structure which enables the adsorption of oxygen molecules and the adsorption of a target substance in addition to the highly efficient adsorption and degradation of a target substance previously discovered (Japanese Patent Application 2001-01-0312). 225034), by performing separate reactions on each reaction simultaneously. That means that, such as in 2 a metal oxide phase having an oxygen-depleted portion of an adjacent ion conduction phase, shown in FIG. 1, prepared by reduction of oxides or from the beginning (preferably in the form of ultrafine particles (having a diameter of about 10 nm to 100 nm) for high reactivity) Contact comes and microspaces of a size of several nm to tens of nm or less are generated around these points of contact so that oxygen molecules in the introduced target gas and the target substance itself are each selectively adsorbed and decomposed into the oxygen-poor part and the metal phase, respectively the energy intake is significantly reduced. If the spaces around the contact points are greater than tens of nm, they will be larger than the average free paths of the gas molecules and the separation and adsorption effect will gradually decrease; or if the areas formed around the pads are greater than 100 nm, that is, if they are significantly larger than the Debye length and the diffusion length of the oxygen vacancy, the selective separation and exclusion performance with respect to the target gas will be reduced.

The metal phase and the oxygen-depleted part normally form contacts due to their production mechanisms; however, they are not necessarily required to be in contact for the above-mentioned selective separation function to apply. That is, even if the oxygen-poor part resulting from the movement of oxygen in the ion-conducting phase due to the contribution of electrons to the metal phase (oxide phase before Reacti on) when current is applied is lost due to effects such as heat shrinkage after its formation contact with the metal phase, this is not a serious obstacle to the selective separation function of the target gas, which is an effect of the present invention.

A Such structure is formed by the chemical reaction system in a reducing atmosphere or under reduced pressure, electricity or a heat treatment in addition to the Heat treatment processes, which are required to form the previously discovered structure (heat treatment in atmosphere at 1400 to 1450 ° C in a system with zirconium oxide and nickel oxide). This means, a necessary condition for the above mentioned Structure is the formation of a reduction phase by applying of electricity at a high temperature of some 100 ° C or more or applying a heat treatment under reduced pressure or in a hydrogen atmosphere or other reducing atmosphere using an oxide that is relatively easy to reduce is.

In This step involves the simultaneous formation of ultrafines Structures for efficient reactions desirable are more advantageous when power is applied. This includes the Making holes, the for the introduction of the target gas, ranging in size from nanometers to one Micrometer due to volume changes in the crystal phase from the oxidation reaction, the formation of ultrafine particles due to the recrystallization of the reduction layer, the formation of oxygen-poor parts in the ionic conduction phase over the entire oxidoreduction and the like.

at The substances that make up such a structure may be a combination of an ion conduction phase and an electron conduction phase, a mixture of conductive Phases or a combination thereof with an ion conduction phase or electron conduction phase. If it is the target substance is nitrogen oxides, is a nickel or other metal phase desirable as a reduction phase, since it shows a highly selective adsorption.

In In the present invention, substances that contain all or one Part of the above-mentioned microreaction areas make up, oxidizing and reducing effects on the target substance on. The above mentioned Metal phase consists for example of ultrafine particles of a Metal phase, which is produced by means of an oxidoreduction, the over one Part or the whole of an electron conductor or electrical Mixed conductor is generated when the above-mentioned chemical reaction system in a reducing atmosphere Electricity or a heat treatment is subjected. Furthermore consists of the above mentioned low-oxygen part of an oxygen-poor layer, which means an oxidoreduction produced in a part or the Entire of an ion conductor or electrical mixed conductor produced if the above mentioned chemical reaction system in a reducing atmosphere electricity or a heat treatment is subjected. The above mentioned Microreaction regions have a structure in which the ionic conductor and the electron conductor directly at least at one point touch or each other while of the manufacturing process.

The Chemical reaction system of the present invention can be prepared be by the contact points in the above-mentioned chemical reaction part the ion conduction phase and the electron conduction phase, which is from a combination of any of an ionic conductor, a Electron conductor and a mixed electrical conductor, in a reducing atmosphere or subjected to electricity or heat treatment under reduced pressure, so micro reaction areas in the above-mentioned chemical reaction part introduce, in which oxidoreductions of the target substance take place. It is in constructing the interfaces the above-mentioned substances desirable, that one or both are in a reduced state.

It is desirable in the present invention that the above-mentioned chemical reaction is a conversion reaction of matter or energy, the above-mentioned target substance is nitrogen oxides, and the above-mentioned chemical reaction is reduction reduction of nitrogen oxides and the above-mentioned chemical reaction the general formula: Mox + xe → M + x / 2O ² → M → xe + M ^{x +} (wherein M is a metal, O is an oxygen atom and e is an electron).

When next becomes the second embodiment of the present invention in more detail explained.

The present invention relates to a chemical reaction system for carrying out a chemical reaction of a target substance, said chemical reaction system composed of a chemical reaction part in which the above-mentioned chemical reaction of the above-mentioned target substance proceeds, and preferably a barrier layer for inhibiting the ionization of oxygen mensetzt.

Of the chemical reaction part for performing chemical reactions a target substance ideally has a reduction phase, the supplying electrons to the elements contained in the target substance To generate ions, an ion conduction phase, the ions from the reduction phase conducts, and an oxidation phase, the electrons of ions, the from the ionic conduction phase releases; of these however, it is possible if necessary, oxidizing and / or reducing catalysts as base units to use those having equivalent characteristics to the above phases, namely Oxidation catalysts, reduction catalysts or Oxidoreduktionskatalysatoren. In this case, these components are not subject to any particular restrictions.

In The present invention is the target substance preferably nitrogen oxides in exhaust gas, and the nitrogen oxides are reduced in the reduction phase, causing oxygen ions produced, which are conducted in the ionic conduction phase. However, the target substance in the present invention is not limited to nitrogen oxides. The chemical reactor of the present invention may be used for production of carbon monoxide by reducing carbon dioxide, to produce a Mixed gases of hydrogen and carbon monoxide from methane or to Production of hydrogen from water can be applied.

The chemical reaction system may be in the form of, for example, a Pipe, a plate or a honeycomb; preferably has However, it in particular one or more through holes with a pair of openings (as in a pipe or honeycomb), wherein in each through hole chemical reaction sites are located.

At the mentioned above chemical reaction part, the reduction phase is porous and should the substance that is the target of the reaction, selectively adsorb. As contained in the reduction in the target substance Elements supplied with electrons be used to generate ions that transmit to the ion conduction phase be, it preferably consists of an electrically conductive substance. For the purpose of promoting the transmission of For electrons and ions, it is desirable that the reduction phase consists of a conductive mixed substance, the features of both electron conduction and ion conduction or that they consist of a mixture of an electron-conducting Substance and an ion-conducting substance. The reduction phase may be a layered structure of at least two or more phases of these Have substances.

The electrically conductive Substance and the ion-conducting substance serving as a reduction layer are not subject to any special restrictions. It can for example, platinum, palladium and other noble metals and nickel oxide, Cobalt oxide, cuprous oxide, lanthanum manganate, lanthanum cobaltite, lanthanum chromite and other metal oxides are used as the electroconductive substance. Barium-containing oxides, zeolites and the like, which are the target substance selectively adsorb also be used as a reduction layer. Preferably at least one or more of the above-mentioned substances as a mixture used with at least one or more ion-conducting substances. Ion conducting substances that may be used include, for example yttria or scandia stabilized zirconia and Cerium (IV) oxide, lanthanum gallate or the like with gadolinium oxide or samarium (III) oxide were stabilized. It is also desirable that the reduction layer consists of a layer structure of at least two or more phases of the above-mentioned substances exist. Especially The reduction layer preferably consists of a layer structure from two phases, an electrically conductive phase consisting of a Precious metal such as platinum or the like, and a mixed phase of nickel oxide or stabilized with yttria or scandium oxide Zirconia.

The Ion conducting phase consists of a solid electrolyte with ionic conductivity and preferably a solid electrolyte having oxygen ion conductivity. Examples of solid electrons with oxygen ion conductivity include yttria or scandia stabilized zirconia and Cerium (IV) oxide or gadolinium oxide or samarium (III) oxide stabilized lanthanum; however, these are not limitations. It is preferred to stabilize with yttria or scandia To use zirconium oxide, which has excellent long-term stability and extremely conductive and strong.

The oxidation phase contains a conductive substance to cause electrons to be released from ions in the ion conduction phase. For the purpose of promoting the transfer of electrons and ions, it is desirable that the oxidation phase be composed of a conductive compound having the characteristics of both electronic conductivity and ionic conductivity, or a mixture of an electron-conductive substance and an ion-conductive substance. The electroconductive substance and the ion-conductive substance used as the oxidizing layer are not particularly limited. For example, platinum, palladium and other noble metals and nickel oxide, cobalt oxide, cuprous oxide, lanthanum manganate, lanthanum cobaltite, lanthanum chromite and other metal oxides are used as the electrically conductive substance. As the ion-conductive substance, zirconia stabilized with yttria or scandia or cerium (IV) oxide or lanthanum gallate stabilized with gadolinia or samarium (III) oxide can be used, for example.

Of the The purpose of the barrier layer is to produce oxygen ions required supply of electrons when oxygen molecules surface adsorbed have been avoided. Alternatively, it is used for the purpose of reoxidation of metals (such as the metal nickel) by reduction reactions of electrically conductive Oxides (such as nickel oxide) by oxygen ions in chemical reaction part has been prepared, provided and has such a material and such a structure that block that Electrons are supplied from the chemical reaction part and in particular that the reduction layer reaches the surface. In this barrier layer it is preferably an ionic conductor, electrical Mixed conductor or insulator, and if it is an electrical Mixed conductor is, is the proportion of electronic conductivity preferably extremely low, there the suppression effect on the electron conduction decreases when the electron conductivity is high is.

at a chemical reaction system in which the chemical reaction part from an oxygen ion conductor (ion conduction phase), a pair from a cathode (reduction phase) and an anode (oxidation phase), with the ionic conduction phase between them, or an oxidation and / or reduction catalyst as base units composed to perform chemical reactions of a target substance, it is a feature of present invention that the ability to ionize and Removing oxygen that hinders the reactions when he is adsorbed by the chemical reaction part, in a reducing one the atmosphere or under reduced pressure either by applying current or an electric field between the cathode and the anode of the above mentioned chemical reaction part or by applying a heat treatment is activated. In the present invention, favorable examples include using a chemical reaction part in which microreaction areas, where oxidoreductions of the target substance take place, into one Part of the chemical reaction part are introduced by in one reducing atmosphere or under reduced pressure, the contact points between a Ion conduction phase and an electron conduction phase resulting from a combination of any of an ionic conductor, an electron conductor or a mixed electrical conductor, electricity or a electric field or a heat treatment be subjected as the chemical reaction part or using a chemical reaction part that has a reduction phase, both for oxygen and the target substance has individual selectivity, and pores with one Size of one Microns or less for efficient delivery and processing of the target substance in the reduction phase, as the chemical reaction part or using a chemical reaction part in which interfaces that from metal phase parts of the electron conduction phase, oxygen poor Parting the ion conduction phase and microspaces (spaces), the the contact points of these surround, exist at the contact points between the electron conduction phase and the ion conduction phase than the ones mentioned above Microreaction areas are formed; or using one chemical reaction part, in which microreaction areas in which the ones mentioned above Oxidoreductions take place in the cathode than the chemical mentioned above Reaction part introduced be as the chemical reaction part and also using a chemical reaction part forming a working electrode layer for Carry out of oxidoreductions in the upper part of the cathode, with micro-regions with a size of nanometers up to one micrometer, in which the above-mentioned oxidoreduction takes place, introduced into this layer be, as the chemical reaction part.

The in the upper part of the cathode within the chemical reaction part arranged working electrode has a structure which makes it possible the adsorption of oxygen molecules and the adsorption of a Target substance in addition for highly efficient adsorption and degradation of a target substance, which have been previously discovered (Japanese Patent Application 2001-225034), by separate substances directed to each reaction simultaneously perform. This means, that one made by reduction of oxides or from the beginning present (preferably in the form of ultrafine particles (with a Diameter from 10 nm to 100 nm) to achieve high reactivity) Metal phase with an oxygen-poor part (a range of about 5 nm, as estimated by calculation from the Debye length) of an adjacent one Ion conducting phase in contact passes and microspaces with a size of a few nm to tens of nm or less around these locations of the contact be generated so that oxygen molecules in the introduced target gas and the target substance itself adsorbed selectively and in the oxygen-poor Part or the metal phase are decomposed, the recording of electrical Energy is significantly reduced.

Such a structure is formed by passing the chemical reaction system in a reducing atmosphere or the like, or a stream Heat treatment in addition to the heat treatment processes required to form the previously discovered structure (heat treatment in the atmosphere at 1400 to 1450 ° C in a system with zirconium oxide and nickel oxide) is subjected. That is, a reduction phase is formed by applying current at high temperatures of several hundred degrees C or more using an oxide which is relatively easy to reduce. In this step, ultrafine structures are desired which are desirable for efficient reactions, including the production of nanometer to micron sized pores suitable for the introduction of the target gas, due to volume changes in the crystal phase from the oxidation reduction, Formation of ultrafine particles by recrystallization of the reduction phase and the formation of oxygen-poor parts in the ion-conducting phase over the entire oxidoreduction. An example of a local structure formed by the above-mentioned methods and desirable for the internal structure of the working electrode layer is shown in FIG 4 shown.

at Substances that make up such a structure are a combination of an ion conduction phase and an electron conduction phase, a mixture of conductive Phases or a combination thereof with an ion conduction phase or electron conduction phase. If it is the target substance is nitrogen oxides, is a nickel or other metal phase desirable as a reduction phase, since it shows a highly selective adsorption.

In addition to Method of introduction a reductor previously described as prior art, it is a process that is used to reactivate a chemical reaction system has been proposed to one, in the carbon or the like already in the chemical reaction system forms a holistic structure and the carbon during the chemical reaction to reduce the oxidized metal phase oxidized (Miura, K., et al., Chemical Engineering Science 56, 1623 (2001)). In these methods, however, reductors are required, and there a reactivation impossible when the reductor is used up, an electrical reaction procedure for the long-term or continuous use of the system more desirable.

In In the present invention, it is only possible to use electricity or the like when the performance of the chemical reaction system is decreased has to oxygen, that of the oxygen-poor part of the chemical Reaction parts was adsorbed, to ionize and pumping to remove. About that It is also possible at the same time to energize the reduction phase again. This way you can the amount of electricity in the present invention much lower be as the one for the pumping of oxygen in conventional galvanic cell systems required amount of electricity.

The Reactivation by pumping oxygen is present in the present Invention performed by in a reducing atmosphere or the like, to the chemical reaction system or voltage is applied or a heat treatment is applied, when the system is at 400 to 700 ° C. In the present invention it is desirable in the above mentioned chemical reaction system to maintain a temperature of 400 to 700 ° C. or raise the temperature within this temperature range or lower and at the same time electricity or an electric field between the cathode and the anode for 1 minute up to 3 hours. In this case, it is desirable Current of 5 mA to 1 A or voltage of 0.5 V to 2.5 V to to cause an electrochemical reaction, and treatment with electricity or an electric field at an oxygen partial pressure from 0% to 21% (in atmosphere) perform. The treatment temperature varies depending on the material and the Structures that make up the system; it is, however, for example a temperature around 560 ° C, though Yttria-stabilized zirconia as a solid electrolyte is used, and a 450 ° C, if Cerium (IV) oxide is used, desirable. The The present invention provides an activation process for a chemical Reaction system ready in which the temperature in the above-mentioned chemical Reaction system at 500 ° C or more, or raised within this temperature range or lowered and in a reducing atmosphere or under reduced pressure, a heat treatment carried out becomes.

In addition to the conditions of the treatment temperature and the component materials the conditions of the amount of applied current, the applied Voltage, the current duration and the oxygen partial pressure or total pressure in the atmosphere variable. For example, when zirconia stabilized with yttria as the electrolyte and nickel oxide and zirconium oxide as working electrode materials will be used, the ability to Disassemble nitrogen oxides by applying 100 mA, 2 V for 1 hour (Oxygen: 10%) restored to pre-treatment levels. Of the Degree of reduction due to oxygen adsorption is after 100 hours continuous operation (without electricity) about 20% and the power can be repeated by means of the above-mentioned current treatment be restored.

Next will be the third embodiment of the present invention explained in more detail.

In the present invention, the solid electrolyte of the oxygen ion conductor is a solid electrolyte having a conductivity of 10 ^-6 Ω- ¹ · cm ^-1 or more at the use temperature. Below 10 ^-6 Ω ^-1 · cm ^-1 , the conductance is so low that an oxidized reducing agent (R) or a reduced oxide (RO _x ) can not be electrochemically reduced or oxidized at an appropriate rate, and the energy loss due to internal combustion Resistance is too high for practical use. Examples of this solid electrolyte of the oxygen ion conductor include the oxides ZrO ₂ , CeO ₂ , Bi ₂ O ₃ and LaGaO ₃ . A ZrO ₂ oxide can be stabilized with Y, Sc or the like. A CeO ₂ oxide can be stabilized with Gd, Sm or the like. Multiple oxygen ion conductors can be used as a composite or laminate. From the viewpoint of stability, ZrO ₂ oxide is particularly desirable for removing nitrogen oxides.

Moreover, in the present invention, the electrode material composed of an electron conductor is a material having a conductivity of 10 ^-6 Ω ^-1 · cm ^-1 or more at the use temperature. Below 10 ^-6 Ω ^-1 · cm ^-1 , the conductance is so low that an oxidized reducing agent (R) or a reduced oxide (RO _x ) can not be electrochemically reduced or oxidized at an appropriate rate, and the energy loss due to internal combustion Resistance is too high for practical use. Examples of this electrode material consisting of an electron conductor include metals, stainless steels, alloys, electron-conductive oxides, graphite, vitreous carbon and other carbons, and the like. In addition, specific examples include platinum, palladium and other noble metals and nickel oxide, cobalt oxide, cuprous oxide, lanthanum manganate, lanthanum cobaltite, lanthanum chromite and other metal oxides. Multiple electron conductors may be used as a composite or laminate. This electrode material may also be compounded with the solid electrolyte of the oxygen ion conductor, or an electric mixed conductor of an oxygen conductor and an electron conductor may be used. Furthermore, the electrode material may also be compounded with a reducing agent or an oxidizing agent. Particularly, from the viewpoint of stability, Au, Pt, Ag, Pd, a Ni oxide, a Cu oxide, a Fe oxide, a Mn oxide or a combination thereof for the purpose of removing nitrogen oxides is desirable.

The reducing agent (R) used in the present invention may be any one of a metal or a suboxide reducing agent having the ability to reduce the oxide AO _x (where x 1/2 is the oxidation number of A), which is the target the reaction is, without being particularly limited; however, desirable examples include Mg, Ca and other alkaline earth metals, Ti, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Zn and other transition metals, Al, Ga, In, Sn and other metals and Ti (III ), V (IV, III, II), Cr (III, II), Mo (IV, III, II), W (V, IV, III, II), Mn (III), Fe (II), Cu ( I) and other suboxides. In particular, from the point of view of selective reactivity, a suboxide or metal, of which 50% or more comprises one or more elements selected from Ni, Cu and Fe, is desirable for removing nitrogen oxides.

The oxide AO _x (where x 1/2 is the oxidation number of A) that can be reduced by the reaction method of the oxidoreduction reactor of the present invention is, for example, organic matter containing oxygen, oxygen, water, nitrogen oxides or the like contained in the oxidoreduction reactor to the reduced product AO _xy (where 0 <y ≤ x) can be reduced. The reduction of the oxide AO _x can proceed to the completely reduced A (y = x) or to the partially reduced AO _xy (where 0 <y <x).

The oxidizing agent (RO _x ) used in the present invention may be any of oxides consisting of oxidizing agent which can oxidize the compound A which is the target of the reaction, without being particularly limited, and examples include Ti, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Zn, Pd, Pt, Rh, Au, Ir and other transition metal oxides and Al, Ga, In, Sn and other metal oxides. In particular, from the point of view of selective reactivity, an oxide of which 50% or more comprises one or more elements selected from Ni, Cu, Ag and Pt is desirable for oxidation reactions of hydrocarbons and organic chlorine compounds.

A compound A which can be oxidized by an oxidation method using the oxidoreduction reactor of the present invention is, for example, organic matter, an organic chlorine compound, hydrogen, carbon monoxide, nitrogen oxides, ammonia or the like mentioned in the above-mentioned Oxidoreduktionsreaktor can be oxidized to AO _y oxides. In particular, alcohol or carboxylic acid may be partially oxidized from a hydrocarbon such as methane, ethane, propane, butane or the like, and organic chlorine compounds such as dioxins may be degraded by oxidation. By controlling the reaction conditions, including reaction time, applied voltage, and the like, it is possible to oxidize compound A to perfectly oxidized AO _y (y = x) or partially oxidized intermediate AO _xy (where 0 <y <x ) to run.

When the oxidoreduction reactor used in the present invention is used as a reduction reactor, a structure such as a reducing agent (R) / electrode / oxygen ion conductor / electrode is used, or when it is used as an oxidation reactor, a structure such as electrode / oxygen ion conductor / electrode / Oxidizing agent (RO _x ) applied. The reducing agent (R) and the electrode may be a mixed phase of the two; The same applies to the electrode and the oxidizing agent (RO _x ). For the purpose of removing nitrogen oxides, the size of the nitrogen oxide reducing agent is in particular in the range of 10 nm to 1 micron. At less than 10 nm, the activity is too strong and other oxides are reduced, making it difficult to selectively reduce nitrogen oxides. At more than 1 μm, the actual surface area of the nitrogen oxide reducing agent is reduced and efficient reduction is difficult to achieve. Moreover, the layer containing the reducing agent (R) or the layer containing the oxidizing agent (RO _x ) may be a porous body having pores to make the oxidation and reduction reactions more efficient.

The nitrogen oxide reducing agent used in the present invention may be produced in the oxidoreduction reactor by contacting one or more of an oxide of oxide, a Cu oxide, a Fe oxide and an Mn oxide with an electrolytic oxygen ion conductor and cathode current is applied to the electron conductor to reduce a portion of the oxide electron conductor. In the oxidoreduction reactor of the present invention, to cause the reducing agent R to restore the oxidized RO _y to the original reducing agent R so as to reduce the oxide AO _x , electrochemically reduce RO _y to R by applying current to the electrode, or otherwise, to cause the oxidant R'O _{x to} restore the reduced R'O _xy to the original oxidant R'O _x so as to oxidize compound A, R'O _xy can be electrochemically added by applying current to the electrode R'O _{x be} oxidized. Restoration of the reducing agent R or the oxidizing agent R'O _x by applying current between the electrodes may be accomplished during the oxidoreduction, or restoration by current application may be performed after a specified time interval.

In the reaction method using the oxidoreduction reactor of the present invention, the operating temperature should be between 300 ° C and 1000 ° C, so that sufficient conductivity of the solid electrolyte, which is the oxygen ion conductor, can be obtained; however, it is also possible to perform the oxidoreduction at a low temperature such as room temperature, heating to the above-mentioned temperature only when the reducing agent R or the oxidizing agent R'O _{x is} electrochemically recovered. In the present invention, since the reducing agent (R) or oxidizing agent (RO _x ) used is any material selected according to the oxidation or reduction potential of the reaction to be carried out in the oxidoreduction reactor, under conditions tuned to the desired reaction, one may highly selective reaction can be achieved.

1 Fig. 10 is a block diagram of a chemical reaction system according to an embodiment of the present invention.

2 shows an example of a local structure that is desirable as the internal structure of the working electrode layer.

3 Fig. 12 is a graph comparing the relationship between the power of removal of nitrogen oxides and the amount of applied current in a chemical reaction system according to the present invention with the results of existing research and the performance of a reactor of a prior application of the present inventors.

4 shows an example of a local structure that is desirable as the internal structure of the working electrode layer.

5 shows how the ability to purify nitrogen oxides is restored by applying current.

Examples of the first embodiment of the present invention will be explained below using the drawings. 1 Fig. 10 is a block diagram of a chemical reaction system according to an embodiment of the present invention. In the chemical reaction part 6 who has the chemical reaction system 7 make up, are a working electrode 2 , a cathode (reduction layer) 3 , an ionic conduction layer 4 and an anode (oxidation layer) disposed in the upstream-downstream direction with respect to the flow of gas that is the target of the reaction, wherein the barrier layer 1 placed upstream of it. In other words, the target gas runs from 1 in the direction 5 ,

2 shows an example of a microreaction range of a desirable internal local Structure in the working electrode layer 2 according to the present invention. The following is a more detailed explanation using nitrogen oxides as the target substance.

example 1

Yttria-stabilized zirconia was used as the ion conducting phase 4 in the form of a disc having a diameter of 20 mm and a thickness of 0.5 mm. The reduction phase 3 was a mixed layer of platinum and zirconium oxide, whereas the working electrode layer 2 was a film consisting of a mixture of nickel oxide and yttria-stabilized zirconia. First, a platinum film was screen-printed on an area of about 1.8 cm ² on one side of the ion conducting phase 4 and formed by heat treatment at 1200 ° C. A mixed film of nickel oxide and yttria-stabilized zirconia was screen printed on the entire surface of the platinum film and formed by heat treatment at 1450 ° C. The mixing ratio of nickel oxide to yttria-stabilized zirconia was 6: 4 moles. After a platinum film was screen-printed on an area of 1.8 cm ² on the other side of the ion conducting phase 4 having a formed reducing phase, it was coated Heat treatment at 1200 ° C formed to produce the oxidation phase 5. The barrier layer 1 was screen printed and heat treated at 1400 ° C using yttria stabilized zirconia about 3 microns thick on the top of the working electrode layer 2 educated. Subsequently, the temperature was raised to 650 ° C while current from 1.2 V to 25 mA through the applied cathode 3 and the applied anode 5 was passed and this temperature was maintained for one hour after stopping the power supply and the system was then cooled.

The method for treating nitrogen oxides with a chemical reaction system of the present invention formed as above is shown below. The chemical reaction system 7 was placed in a target gas, the reduction phase 3 and the oxidation phase 5 were fixed with platinum wires as lead wires and connected to a DC power source, and DC voltage was applied to start the current flow. The evaluation was carried out at a reaction temperature range of 500 ° C to 600 ° C. A helium-balanced exhaust gas sample containing 1000 ppm of nitrogen monoxide and 2% of oxygen was supplied at a flow rate of 50 ml / min as the target gas. The nitrogen oxide concentration in the target gas before and after the flow to the chemical reactor was measured with a chemiluminescence meter for NO _x , while the nitrogen and oxygen concentrations were measured by gas chromatography. The exclusion rate of nitrogen oxides was derived from the amount of reduction of nitrogen oxides, and the current density and electrical energy consumption were measured when the exclusion rate reached 50%.

The reaction temperature of the chemical reactor was raised to 600 ° C, and power was supplied to the chemical reaction part. As the amount of electricity increased, the nitrogen oxide exclusion rate increased and the nitrogen oxides dropped to about 50% when the current density was 31 mA / cm ² and the energy consumption was 61 mW / cm ² . In the 3 For example, the performance of a chemical reactor of the present invention is shown in comparison with the performance of a reactor of a prior application and the results of existing research. It can be seen from this figure that the performance of the chemical reactor of the present application surpasses the results of existing research.

Example 2

In the final stage excitation and heating process of producing a chemical reaction system as in Example 1, four cycles were performed in which 1.2 V to 25 mA current was passed between the cathode 3 and the anode 5 was applied while the temperature was raised to 650 ° C and held for 1 hour after stopping the power supply, followed by gradual cooling, and the relationship between the number of cycles and the ability to process nitrogen oxides was examined. For 2 cycles, a nitrogen oxide removal rate of 50% was achieved at a current density of 25 mA / cm ² and an electrical energy consumption of 49 mW / cm ² , while for 3 cycles a current density of 24 mA / cm ² and an electrical energy consumption of 47 mW / cm ² fell off; however, at 4 cycles, the results were similar to those achieved with 3 cycles.

Example 3

Changes in reactivity in a chemical reaction system prepared as in Example 1 were examined in terms of the amount of coexisting oxygen that impeded the reaction and the concentration of nitrogen oxides that was the target substance. The current density and the electrical energy consumption at 50% reduction were measured under the same experimental conditions as in Example 1 (a) with 2% to 10% increased oxygen amount and (b) 1000 ppm down to 500 ppm reduced nitrogen oxide concentration. Which he Results were (a) current density of 55 mA / cm ² and electrical energy consumption of 150 mW / cm ² and (b) current density of 20 mA / cm ² and electrical energy consumption of 37 mW / cm ² , indicating that the relative processability is improved in the chemical reaction system of the present invention even with a large amount of coexisting oxygen, while at a low nitrogen oxide concentration, a drastic performance increase is recognized.

Examples of the second embodiment of the present invention will be explained below using the figures. 1 Fig. 10 is a block diagram of a chemical reaction system according to an embodiment of the present invention. In the chemical reaction part 6 who has the chemical reaction system 7 The working electrode, the cathode (reduction layer), the ion conducting layer and the anode (oxidation layer) are arranged in the upstream-downstream direction from 2 to 5 with respect to the flow of gas which is the target of the reaction , wherein the barrier layer 1 placed upstream of it. In other words, the target gas runs from 1 in the direction 5.

in the The following is a more detailed one Statement, in which nitrogen oxides are used as the target substance.

Example 4

Yttria-stabilized zirconia was used as the ion conducting phase 4 in the form of a disc having a diameter of 20 mm and a thickness of 0.5 mm. The reduction phase 3 was a mixed layer of platinum and zirconium oxide, whereas the working electrode layer 2 was a film consisting of a mixture of nickel oxide and yttria-stabilized zirconia. First, a platinum film was screen-printed on an area of about 1.8 cm ² on one side of the ion conducting phase 4 and formed by heat treatment at 1200 ° C. A mixed film of nickel oxide and yttria-stabilized zirconia was screen printed on the entire surface of the platinum film and formed by heat treatment at 1450 ° C. The mixing ratio of nickel oxide to yttria-stabilized zirconia was 6: 4 moles. After a platinum film was screen-printed on an area of 1.8 cm ² on the other side of the ion conducting phase 4 having a formed reducing phase, it was coated Heat treatment at 1200 ° C formed to produce the oxidation phase 5. The barrier layer 1 was screen printed and heat treated at 1400 ° C using yttria stabilized zirconia about 3 microns thick on the top of the working electrode layer 2 educated. Subsequently, the temperature was raised to 650 ° C while current from 1.2 V to 25 mA through the cathode 3 and the anode 5 was passed and this temperature was maintained for one hour after stopping the power supply and the system was then cooled.

The method for treating nitrogen oxides with a chemical reaction system of the present invention formed as above is shown below. The chemical reaction system 7 was placed in a target gas, the reduction phase 3 and the oxidation phase 5 were fixed with platinum wires as lead wires and connected to a DC power source, and DC voltage was applied to start the current flow. The system performance was evaluated at 600 ° C current supply and no current supply at a reaction temperature of 350 ° C. A helium-balanced exhaust gas sample containing 1000 ppm of nitrogen monoxide and 2% of oxygen was supplied at a flow rate of 50 ml / min as the target gas. The nitrogen oxide concentration in the target gas before and after the flow to the chemical reaction system was measured by a chemiluminescence meter for NO _x , while the nitrogen and oxygen concentrations were measured by gas chromatography. The purification rate of nitrogen oxides was derived from the amount of reduction of nitrogen oxides, and the current density and the electric energy consumption were measured when the purification rate reached 50%.

That is, the chemical reactor was heated to a reaction temperature of 600 ° C at the start of the measurement, and power was supplied to the chemical reaction part. At this time, the nitrogen oxide purification rate increased with increasing amount of current, and the nitrogen oxides decreased to about 50% when the current density was 31 mA / cm ² and the energy consumption was 61 mW / cm ² .

The power supply to this chemical reaction system was stopped 1 hour after the start of this, while the measurement of the decomposition rate of nitrogen oxides was continued. The rate of degradation of nitrogen oxides dropped by about 10% immediately after power adjustment, but then tended to decrease slowly, decreasing by as little as 5% or less after a total of 5 days (120 hours) of continuous measurement, indicating that the exclusion rate in the Time course decreased. When the amount of electrical energy needed for a total nitrogen exclusion reaction of 120 hours was compared with values calculated at a 35% exclusion rate It has been found that this has been reduced by about 1/84 or less with the present invention as required by continuous power supply.

Example 5

In order to examine the applicability to conditions of actual use, the ability to remove nitrogen oxides at 2% to 10% increased oxygen content and from 1000 ppm to 500 ppm reduced concentration of nitrogen oxides in a chemical reaction system of the same construction as in Example 4 was examined. The system was energized 3 times for 10 minutes each under the same conditions of temperature and electrical energy as in Example 4. Like in the 5 The degradation rate of nitrogen oxides immediately after starting the measurement decreased by 15% or more and dropped to a nitrogen oxide degradation rate of less than 30% about 20 hours after starting the measurement, but then gradually decreased to about 100% Hours in an approximate balance. After 200 hours, approximately the same changes in nitrogen oxide degradation rate were achieved by re-applying current over time.

Example 6

Activation of the system by treatment in a reducing atmosphere was evaluated in a chemical reaction system of the same construction as in Example 4. In a chemical reaction system that consumed about 68 mW / cm ² for 50% nitrogen oxide removal, with 2% coexisting oxygen, a system operating temperature of 650 ° C and a nitrogen oxide concentration of 1000 ppm, the temperature was 48 hours after stopping from the power supply (wherein the nitrogen oxide degradation rate had fallen to 38% at this time) was raised to 800 ° C, a reducing gas of 5% hydrogen and 95% argon was supplied for 10 hours and the nitrogen oxide purification performance was measured, it was found that the power was around had increased by about 2%.

When next the third embodiment of the present invention explained in detail based on examples; the However, the present invention is not limited only to these examples.

Example 7

With Yttria stabilized zirconia was used as a solid electrolyte with oxygen ion conductivity in the form of a disc with a diameter of 20 mm and a Strength of 0.5 mm used. The electrode layer was around a composite of platinum and stabilized with yttria Zirconia with a volume ratio of 40:60. The reducing agent layer was a composite of iron, platinum and yttria stabilized Zirconia with a volume ratio of 30:30:40 and was as the upper layer of the above-mentioned electrode layer. The electrode layer, which was the counter electrode, was stabilized as a composite of platinum and yttria Zirconia with a volume ratio of 60:40 on a too the opposite surface the solid electrolyte disk made equal area.

An oxygen reduction reactor made in this manner was used to synthesize H ₂ by reducing H ₂ O in the presence of 10% CO ₂ . By applying current between the electrodes under temperature conditions of 400 to 800 ° C, even in the presence of CO _{2, it was} possible to selectively reduce H ₂ O and produce H ₂ at a conversion rate of 90%. In addition, current was applied to the electrodes to restore the reducing agent, the power supply was stopped, the same H ₂ O was selectively reduced at an H ₂ conversion rate of 50 to 80% and the reducing agent was restored by applying current between the electrodes, when the turnover rate fell to 50% or less. After the restoration, the power supply was stopped and a reaction was conducted as above, and it was possible to make H ₂ again at a conversion rate of 50 to 80%.

Example 8

Yttria-stabilized zirconia was used as a solid electrolyte with oxygen ion conductivity in the form of a disc having a diameter of 20 mm and a thickness of 0.5 mm. The electrode layer was a composite of platinum and yttria-stabilized zirconia with a volume ratio of 40:60. The nitrogen oxide reducing agent layer was a composite of nickel oxide and yttria-stabilized zirconia having a volume ratio of 40:60, and was prepared as the upper layer of the above-mentioned electrode layer. The electrode layer, which was the counter electrode, was fabricated as a composite of platinum and yttria-stabilized zirconia having a volume ratio of 60:40 on an area equal in area to the opposite surface of the solid electrolyte disk. Current was applied between the electrodes at 500 ° C to form some of the nickel oxide of the nitrogen oxide reductant layer to nickel metal part 100 nm in size and to form the final nitrogen oxide reductant layer.

1000 ppm NO as the nitrogen oxides were reduced and removed in the presence of 5% O ₂ by means of an oxidoreduction reactor prepared in this way. NO was selectively reduced even in the presence of O ₂ by applying current between the electrodes under temperature conditions of 400 to 700 ° C at a conversion rate of 70%. In addition, current was applied to the electrodes to restore the reducing agent, the power supply was stopped, the same NO was selectively reduced at a conversion rate of 50 to 80%, and the reducing agent was restored by applying current between the electrodes when the conversion rate was 50 % or less fell. After the restoration, the power supply was stopped and a reaction was conducted as above, and it was possible to make NO again at a conversion rate of 50 to 80%.

Example 9

With Yttria stabilized zirconia was used as a solid electrolyte with oxygen ion conductivity in the form of a disc with a diameter of 20 mm and a Strength of 0.5 mm used. The electrode layer was a composite of lanthanum manganate and yttria stabilized Zirconia with a volume ratio of 50:50. The nitrogen oxide reducing agent layer was a composite of nickel oxide and yttria stabilized Zirconia with a volume ratio of 40:60 and was reported as the upper layer of the above mentioned Electrode layer produced. The electrode layer as the counter electrode was thus made from La-Sr-Ca-Fe-O, that they have one to the opposite surface of the Solid electrolyte disk had the same size surface. Between the electrodes was at 500 ° C Power applied to some of the nickel oxide of the nitric oxide reductant layer to convert into nickel metal particles with a size of 50 nm and to form the final nitrogen oxide reducing agent layer.

1000 ppm of NO as the nitrogen oxides were reduced and removed in the presence of 10% O ₂ with an oxidoreduction reactor prepared in this way. Even in the presence of O ₂ , it was possible to selectively reduce NO at a conversion rate of 65% by applying current between the electrodes under temperature conditions of 400 to 700 ° C. In addition, current was applied to the electrodes to restore the reducing agent, the power supply was stopped, the same NO was selectively reduced at a conversion rate of 50 to 80%, and the reducing agent was restored by applying current between the electrodes when the conversion rate was 50 % or less fell. After the restoration, the power supply was stopped and a reaction was conducted as above, and it was possible to make NO again at a conversion rate of 50 to 80%.

Example 10

With Yttria stabilized zirconia was used as a solid electrolyte with oxygen ion conductivity in the form of a disc with a diameter of 20 mm and a Strength of 0.5 mm used. The electrode layer was around a composite of platinum and stabilized with yttria Zirconia with a volume ratio of 40:60. The oxidation layer was a composite of silver oxide, platinum and yttria stabilized Zirconia with a volume ratio of 30:30:40 and was as the upper layer of the above-mentioned electrode layer. The Electrode layer, which was the counter electrode, was stabilized as a composite of platinum and yttria Zirconia with a volume ratio of 60:40 on a too the opposite surface the solid electrolyte disk made equal surface area.

CH ₃ OH was synthesized by partial oxidation of CH ₄ in the presence of 5% CO using an oxidoreduction reactor prepared in this way. By applying current between the electrodes under temperature conditions of 400 to 600 ° C, even in the presence of CO, it was possible to produce CH ₃ OH by selective oxidation of CH ₄ at a conversion rate of 95%. In addition, current was applied between the electrodes to restore the oxidant, the power supply was stopped, the same CH ₄ was selectively oxidized to produce CH ₃ OH at a conversion rate of 60 to 80%, and current was passed between the electrodes to to restore the oxidant when the conversion rate fell to 60% or less. After the restoration, the power supply was stopped, and when the same reaction as above was carried out, it was possible to produce again CH ₃ OH at a conversion rate of 60 to 80%.

Example 11

Yttria-stabilized zirconia was used as a solid electrolyte with oxygen ion conductivity in the form of a disc having a diameter of 20 mm and a thickness of 0.5 mm. The electrode layer was a composite of platinum and yttria-stabilized zirconia with a volume ratio of 40:60. The oxidation layer was an Ver Composite of copper (I) oxide, platinum and yttria-stabilized zirconia having a volume ratio of 40:30:30 was prepared as the upper layer of the above-mentioned electrode layer. The electrode layer, which was the counter electrode, was fabricated as a composite of lanthanum manganate and yttria-stabilized zirconia having a volume ratio of 60:40 on a surface area of equal size to the opposite surface of the solid electrolyte disk.

dioxin was in the presence of 10% CO using a prepared as above Oxidoreduction reactor degraded by oxidation. By applying of current between the electrodes under temperature conditions of 400 to 600 ° C Even in the presence of CO, it was possible to have dioxin at a conversion rate of 80% to selectively oxidize and degrade. In addition, electricity was between applied to the electrodes to restore the oxidant, the power supply was stopped, the same dioxin was with a Turnover rate of 40 to 70% selectively degraded by oxidation, and electricity was passed between the electrodes to the oxidizing agent restore if the turnover rate fell to 40% or less. After restoration, the power was stopped and when the same reaction was done as above, it was possible again Dioxin with a conversion rate of 40 to 70% by oxidation.

Example 12

An Sm-stabilized CeO ₂ oxide was used as a solid electrolyte with oxygen ion conductivity in the form of a disc having a diameter of 20 mm and a thickness of 0.5 mm. The electrode layer was a composite of lanthanum manganate and Sm-stabilized CeO ₂ oxides having a volume ratio of 50:50. The oxidizing layer was a composite of silver oxide, tungsten oxide and Sm-stabilized CeO ₂ oxides having a volume ratio of 20: 20: 30: 30, and was prepared as the upper layer of the above-mentioned electrode layer. The electrode layer, which was the counter electrode, was fabricated as a composite of lanthanum manganate and Sm-stabilized CeO ₂ oxides having a volume ratio of 60:40 on an area equal in area to the opposite surface of the solid electrolyte disk.

CH ₃ COOH was synthesized by partial oxidation of CH ₃ CH ₂ OH in the presence of 5% CH ₄ using an oxidoreduction reactor as prepared above. By applying current between the electrodes under temperature conditions of 400 to 600 ° C, it was even in the presence of CH ₄ possible to produce CH ₃ COOH by selective partial oxidation of CH ₃ CH ₂ OH at a conversion rate of 70%. In addition, current was applied between the electrodes to restore the oxidant, the current supply was stopped, the same CH ₃ CH ₂ OH was selectively partially oxidized to produce CH ₃ COOH at a conversion rate of 50 to 70%, and current was between the Electrodes passed to restore the oxidant when the conversion rate fell to 50% or less. After the restoration, the power supply was stopped, and when the same reaction as above was carried out, it was possible to produce again CH ₃ COOH at a conversion rate of 50 to 70%.

• (1) Es kann ein chemisches Reaktionssystem bereitgestellt werden, das eine Zielsubstanz selbst in Gegenwart von überschüssigem Sauerstoff, der die chemische Reaktion der Zielsubstanz stört, effizient verarbeiten kann.
• (2) Die zum Abbauen von Stickstoffoxiden erforderliche Strommenge kann verringert werden und Stickstoffoxide können bei geringer elektrischer Energieaufnahme effizient ausgeschlossen werden.
• (3) Mikroreaktionsbereiche, an denen Oxidations- und Reduktionsreaktionen einer Zielsubstanz stattfinden, können in einen Teil des chemischen Reaktionsteils des oben erwähnten chemischen Reaktionssystems eingeführt werden.
• (4) Es kann ein chemisches Reaktionssystem bereitgestellt werden, das einen chemischen Reaktionsteil aufweist, wobei Grenzflächen, die aus Metallphasenteilen der Elektronenleitungsphase, sauerstoffarmen Teilen der Ionenleitungsphase und Mikroräumen (Zwischenräumen), die die Kontaktstellen dieser umgeben, bestehen, an den Kontaktstellen zwischen der Elektronenleitungsphase und der Ionenleitungsphase ausgebildet werden.

As discussed above, the first embodiment of the present invention achieves the following effects.

• (1) A chemical reaction system can be provided which can efficiently process a target substance even in the presence of excess oxygen which interferes with the chemical reaction of the target substance.
• (2) The amount of electricity required to decompose nitrogen oxides can be reduced, and nitrogen oxides can be efficiently excluded at a low electric power consumption.
• (3) Microreaction regions where oxidation and reduction reactions of a target substance take place can be introduced into a part of the chemical reaction part of the above-mentioned chemical reaction system.
• (4) A chemical reaction system may be provided which has a chemical reaction part, wherein interfaces consisting of metal phase parts of the electron conduction phase, oxygen-poor parts of the ion conduction phase, and micro-spaces (spaces) surrounding the contact points thereof, at the contact points between the electron conduction phase and the ion conduction phase are formed.

• (1) Es kann ein chemisches Reaktionssystem bereitgestellt werden, das eine Zielsubstanz bei geringer elektrischer Energieaufnahme selbst in Gegenwart von überschüssigem Sauerstoff, der die chemische Reaktion der Zielsubstanz stört, effizient verarbeiten kann.
• (2) Stickstoffoxide können bei geringer elektrischer Energieaufnahme effizient ausgeschlossen werden.
• (3) Das chemische Reaktionssystem kann reaktiviert werden.
• (4) Es kann ein energiesparendes elektrochemisches Reaktionssystem bereitgestellt werden, wobei der chemische Reaktionsteil reaktiviert und durch Anlegen von Strom oder eines elektrischen Felds in Zeitintervallen verwendet werden kann.

Moreover, with the second embodiment of the present invention, the following effects are achieved.

• (1) A chemical reaction system can be provided which can efficiently process a target substance at a low electric energy consumption even in the presence of excess oxygen which interferes with the chemical reaction of the target substance.
• (2) Nitrogen oxides can be efficiently excluded with low electrical energy consumption.
• (3) The chemical reaction system can be reactivated.
• (4) An energy-saving electrochemical reaction system can be provided wherein the chemical reaction part can be reactivated and used by applying current or an electric field at time intervals.

• (1) Es kann ein Reaktionsverfahren zum Oxidieren oder Reduzieren mit hoher Selektivität unter Verwendung eines Oxidoreduktionsreaktors ohne Erfordernis einer Zufuhr oder eines Austauschs eines Reduktors oder Oxidans bereitgestellt werden.
• (2) Da im Reaktionsverfahren, in dem der Oxidoreduktionsreaktor der vorliegenden Erfindung verwendet wird, das Reduktionsmittel oder Oxidationsmittel gemäß der Reaktion von verschiedenen Substanzen mit Fähigkeit zur Oxidation oder Reduktion ausgewählt wird, kann eine gewünschte Substanz, wie beispielsweise organische Materie, eine organische Chlorverbindung, Wasserstoff, Kohlenmonoxid, Ammoniak, Stickstoffoxide oder dergleichen, mit hoher Selektivität oxidiert werden.
• (3) Die vorliegende Erfindung kann beispielsweise zum Synthetisieren nützlicher Substanzen, wie beispielsweise Wasserstoff, Methanol, Essigsäure und dergleichen, um Verunreinigungen zu entfernen, und zum Entfernen von Schadstoffen, wie beispielsweise Dioxinen und Stickstoffoxiden in Abgas, verwendet werden.
• (4) Da im Verfahren der vorliegenden Erfindung das Reduktionsmittel oder Oxidationsmittel durch Anlegen von Strom wiederhergestellt werden kann, kann ein wartungsarmes Reaktionsverfahren bereitgestellt werden, in dem diese nicht ausgetauscht werden müssen.

Moreover, Embodiment 3 of the present invention relates to a reaction process for oxidation and reduction reactions, and the effects described below are achieved with the present invention.

• (1) A reaction method for oxidizing or reducing with high selectivity can be provided by using an oxidoreduction reactor without the necessity of supplying or exchanging a reducer or oxidant.
• (2) In the reaction method in which the oxidoreduction reactor of the present invention is used, since the reducing agent or oxidizing agent is selected according to the reaction of various substances capable of oxidation or reduction, a desired substance such as organic matter, an organic chlorine compound, Hydrogen, carbon monoxide, ammonia, nitrogen oxides or the like can be oxidized with high selectivity.
• (3) The present invention can be used, for example, for synthesizing useful substances such as hydrogen, methanol, acetic acid and the like to remove impurities, and for removing pollutants such as dioxins and nitrogen oxides in exhaust gas.
• (4) In the method of the present invention, since the reducing agent or oxidizing agent can be recovered by applying current, a low-maintenance reaction method can be provided in which they need not be replaced.

SUMMARY

The The present invention relates to a chemical reaction system for efficient exclusion of nitrogen oxides at low energy intake, when in exhaust gas excess oxygen a method of using this system, an activation method for this System and reaction process for oxidizing or reducing with high selectivity by using an oxidoreduction reactor without requirement of feeding or replacing a reductant or oxidant.

1

junction

2

Working electrode layer

3

cathode (Reduction phase)

4

Ion conduction phase

5

anode (Oxidation phase)

6

chemical reaction part

7

chemical reaction system

Claims (39)

Chemical reaction system for performing chemical Reactions of a target substance that has a chemical reaction part comprising an oxygen ion conductor (ion conduction phase) and two electrodes, a cathode (reduction phase) and an associated anode (Oxidation phase), with the ionic conduction phase between them is composed of basic units, with microreaction areas, where oxidoreductions of a target substance take place, into one Part of the chemical reaction part are introduced by in one reducing atmosphere or under reduced pressure on the points of contact between the ion conduction phase and an electron conduction phase, which is from a combination of any of an ionic conductor, an electron conductor or composed of an electric mixed conductor, in the chemical reaction part Current or voltage applied or a heat treatment is applied. A chemical reaction system according to claim 1, wherein Interfaces, that of a metal phase of the electron conduction phase, an oxygen-poor part the ion conduction phase and microspaces (spaces), the the contact points of these surround exist as the microreaction areas at the points of contact between the electron conduction phase and the ion conduction phase are formed. A chemical reaction system according to claim 1, wherein Microreaction areas where the oxidoreductions take place be introduced into the cathode. A chemical reaction system according to claim 1, wherein a working electrode layer for controlling oxidoreductions in the the upper part of the cathode is formed and microreaction areas with a size of nanometers up to a micrometer, at which the oxidoreductions take place, introduced into this layer become. A chemical reaction system according to claim 1, wherein a substance which makes up all or part of the microreaction regions has an oxidizing or reducing effect on the target substance Has effect. A chemical reaction system according to claim 1, wherein the metal phase consists of ultrafine particles of a metal phase, which was produced by an oxidoreduction, which over one Part or the whole of an electron conductor or an electric Mixed conductor was induced by the chemical reaction system in a reducing atmosphere Electricity or a heat treatment was subjected. A chemical reaction system according to claim 1, wherein the oxygen-poor part consists of an oxygen-poor layer, which was produced by an oxidoreduction, which over one Part or the whole of an electron conductor or an electric Mixed conductor was induced by the chemical reaction system in a reducing atmosphere Electricity or a heat treatment was subjected. A chemical reaction system according to claim 1, which is a Structure in which the inner conductor and the electron conductor touching each other at at least one location to the microreaction areas or in which they touch each other in the manufacturing process of this. A chemical reaction system according to claim 1, wherein a barrier layer of a substance that breaks the electron conduction can be involved on the way, on which the target substance from the surface the galvanic cell to the room where the chemical reaction takes place moved along. A chemical reaction system according to claim 1, wherein the chemical reaction is a conversion reaction of matter or energy. A chemical reaction system according to claim 1, wherein the target substance is nitrogen oxides. A chemical reaction system according to claim 10, wherein the chemical reaction is the reduction of nitrogen oxides. A chemical reaction system according to claim 9, wherein in the chemical reaction system, a chemical reaction represented by the following general formula: Mox + xe → M + x / 2O ² M → xe + M ^{x +} (where M is a metal, O is an oxygen atom and e is an electron). Method of manufacturing in any the claims 1 to 13 defined chemical reaction system, the introduction of Microreaction areas where oxidoreductions of a target substance take place in a chemical reaction part, putting in a reducing Atmosphere on the locations of contact between an ion conduction phase and a Electron conduction phase resulting from a combination of arbitrary an inner conductor, an electron conductor and an electric Mixed conductor composed in the chemical reaction part current applied or a heat treatment is applied. The method of claim 14, wherein when the substances touching each other, around an interface to form one of these or both in a reduced State are. Method of activating a chemical reaction system, wherein in the chemical reaction system according to claim 1 of metal phase parts of a Electron conduction phase or an electric mixed conduction phase and oxygen-depleted portions of an ionic conduction phase or a mixed-phase electrical phase Couples are formed. Chemical reaction system in which the chemical Reaction part from 1) an oxygen ion conductor (ionic conduction phase), a cathode (reduction phase) and an associated anode (oxidation phase), with the ionic conduction phase between them, or 2) an oxidation and / or reduction catalyst as basic units composed to perform chemical reactions of a target substance, wherein the chemical reaction part in a reducing atmosphere or under reduced pressure, current or voltage or a heat treatment is subjected to the ability for ionizing and removing oxygen, which prevents reactions when adsorbed by the chemical reaction part, activate. A chemical reaction system according to claim 17, wherein a chemical reaction part containing a reduction layer, both for oxygen and a target substance has selectivity, and holes with a size of one Microns or less, which allows for efficient delivery and processing of the target substance in the reduction phase are required, as the chemical Reaction part is used. A chemical reaction system according to claim 17, wherein a chemical reaction part having microreaction regions where oxidoreductions of a target substance take place and which are in egg NEN part of the chemical reaction part were introduced by current or voltage in a reducing atmosphere or under reduced pressure to the points of contact between an ion conducting phase and an electron conducting phase, which consists of a combination of any of an ionic conductor, an electron conductor and a mixed electric conductor or a heat treatment has been applied when the chemical reaction part is used. A chemical reaction system according to claim 19, wherein a chemical reaction part is used in the interfaces, the of metal parts of the electron conduction phase, oxygen-poor parts the ion conduction phase and microspaces (spaces), the Surrounding the places of contact of these exist as the microreaction areas be formed. A chemical reaction system according to claim 19, wherein a chemical reaction part having microreaction regions, where the oxidoreductions take place and those in the cathode introduced were used when the chemical reaction part. A chemical reaction system according to claim 17, wherein a chemical reaction part, which is a working electrode layer for controlling oxidoreductions in the upper part of the cathode and microreaction regions with a size of nanometers up to to a micrometer where the oxidoreductions take place and that introduced into this layer were used when the chemical reaction part. A chemical reaction system according to claim 17, wherein the target substance is nitrogen oxides. A chemical reaction system according to claim 22, wherein the chemical reaction is the reduction of nitrogen oxides. Method of using one in any one the claims 17 to 24 defined chemical reaction system for performing chemical reactions of a target substance, keeping the temperature of the system at 400 to 700 ° C or raising or lowering the temperature within this temperature range in the chemical reaction system and the application of electricity or Voltage in time intervals to the chemical reaction part to activate, includes. Method of activating one in any one the claims 17 to 24 defined chemical reaction system for performing chemical reactions of a target substance, keeping the temperature of the system at 400 to 700 ° C or raising or lowering the temperature within this temperature range in the chemical reaction system and applying a current or voltage treatment between the cathode and the anode for 1 minute up to 3 hours. Method for activating a chemical reaction system according to claim 26, wherein by applying current of 5 mA to 1 A. or voltage of 0.5V to 2.5V elicited an electrochemical reaction becomes. Method for activating a chemical reaction system according to claim 26, wherein the power or voltage treatment at an oxygen partial pressure of 0% to 21% (in atmosphere) is performed. Method of activating one in any one the claims 17 to 24 defined chemical reaction system for performing chemical reactions of a target substance, keeping the temperature of the system at 500 ° C or more or raising or lowering the temperature within this temperature range in the chemical reaction system and the heat treatment of the system in a reducing atmosphere or under reduced pressure Pressure includes. A reaction process which is an oxidoreduction process using an oxidoreduction reactor composed of a solid electrolyte oxygen ion conductor and at least one electrode consisting of an electron conductor, and forming the cathode by an oxide reduction of a Oxide AO _x and a reducing agent (R) based on the reaction formula AO _x + R → RO _y + AO _xy with the reducing agent (R) and the reduction product AO _xy (wherein 0 <y ≤ x) was supplied, or the production of the anode which supplies the oxidizing agent (R'O _x ) and the oxide AO _y by an oxidoreduction of a compound A and an oxidizing agent (R'O _x ) based on the reaction formula A + R'O _x .R'O _xy + AO _y was included. A reaction process according to claim 30, wherein the cathode is supplied with a reducing agent (R) consisting of a metal or suboxide, (1) oxide AO _x (wherein x is the oxidation number of A) introduced into the reactor and the Reduction product AO _xy (where 0 <y ≤ x) is prepared by an oxide reduction of the oxide AO _x and the reducing agent (R) based on the reaction formula AO _x + R → RO _y + AO _xy and (2) supplied to the electrode current and the oxidized reducing agents (RO _y ) by the electrochemical reaction, the is represented by the reaction formulas _y 2e ^- + RO _y → R + yO ^2- (cathode) and yO ^{2 -} → y 1/2 O ↑ + y 2e ^- (anode) is reduced to restore the reducing agent (R). A reaction process according to claim 31, wherein the electrode is supplied with current either after or simultaneously with the production of the reduction product AO _xy (where 0 <y ≤ x) by an oxide reduction of the oxide AO _x and the reducing agent (R) to form the reducing agent (R). restore. The reaction method according to claim 32, wherein the reducing agent (R) is a nitrogen oxide reducing agent and a reduction product of N ₂ is an oxidoreduction of the nitrogen oxide reducing agent and the nitrogen oxide NO _x based on the reaction formula NO _x + R → RO _x + x / 2N _{2 is} made to remove the NO _x . The reaction process of claim 33, wherein the oxidoreduction reactor a nitrogen oxide reducing agent consisting of metals or suboxides of which 50% or more of one or more of Ni, Cu and Fe selected Elements include an electrode made of an electron conductor which is one or more of Au, Pt, Ag, Pd, compounds selected from Ni oxide, Cu oxide, Fe oxide and Mn oxide and a solid electrolyte oxygen ion conductor made of zirconia consists of. A reaction method according to claim 33 or 34, wherein the size of the nitrogen oxide reducing agent 10 nm to 1 μm is. The reaction method of claim 33, wherein an oxide electron conductor, which is one or more of a Ni oxide, a Cu oxide, a compound selected from Fe oxide and Mn oxide, contacted with a solid electrolyte oxygen ion conductor and cathode current is supplied to the electron conductor to form part of Reduce oxide electron conductor and a nitrogen oxide reducing agent with a size of 10 nm to 1 μμm to form. A reaction process according to claim 30, wherein the anode is supplied with an oxidant (R'O _x ) consisting of an oxide, (1) compound A is introduced into the reactor and oxide AO _{y is} obtained by an oxidoreduction of the compound A and the oxidizing agent ( R'O _x ) is prepared on the basis of the reaction formula A + R'O _x → R'O _xy + AO _y and (2) the electrode is supplied with current and the reduced oxide R'O _xy by the electrochemical reaction provided by the reaction formulas yO ^2- + R'O _xy → R'O _x + y2e ^- (anode) and y2e ^- + O ₂ → y2O ^2- (cathode) is oxidized to recover the oxidant (R'O _x ). A reaction process according to claim 37, wherein power is supplied to the electrode either after or simultaneously with the production of the oxide AO _y by an oxidoreduction of the compound A and the oxidant (R'O _x ) to recover the oxidant (R'O _x ). A reaction method according to claim 37 or 38, wherein it is the compound A to a hydrocarbon or organic Chlorine compound is.